EP1456281B1 - Procede de recuperation d'un polymere a partir d'une solution - Google Patents

Procede de recuperation d'un polymere a partir d'une solution Download PDF

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Publication number
EP1456281B1
EP1456281B1 EP02791786A EP02791786A EP1456281B1 EP 1456281 B1 EP1456281 B1 EP 1456281B1 EP 02791786 A EP02791786 A EP 02791786A EP 02791786 A EP02791786 A EP 02791786A EP 1456281 B1 EP1456281 B1 EP 1456281B1
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EP
European Patent Office
Prior art keywords
solvent
polymer
process according
medium
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP02791786A
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German (de)
English (en)
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EP1456281A1 (fr
Inventor
Bernard Vandenhende
François VAN LOOCK
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Solvay SA
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Solvay SA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
    • C08J11/08—Recovery or working-up of waste materials of polymers without chemical reactions using selective solvents for polymer components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/122—Pulverisation by spraying
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/14—Powdering or granulating by precipitation from solutions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention relates to a process for recovering a polymer in solution.
  • Polymers are abundantly used in various forms, mainly in solid form. However, it often occurs that, at a given moment in their existence, they are in solution in a solvent from which they then need to be extracted. Thus, the obstacle of polymer solutions is encountered at the end of certain ("solution") polymerization processes, during certain recycling processes, during the cleaning of certain plants for manufacturing polymer-based articles or paints, etc.
  • solution certain
  • the recovery of the polymer in solid form from a solution generally involves at least one step of evaporation of the solvent. However, this operation is often expensive on account of its energy consumption, and it does not necessarily lead to polymer particles of adequate particle size. In addition, these polymer particles often have an appreciable residual solvent content.
  • Patent application WO 01/070865 to the inventor describes a method for recycling a plastic material such as PVC or PVDC using a solvent and a non solvent. This process uses azeotropic distillation for recovering the polymer in solid form, and not an atomization step or a gas that vaporises the solvent.
  • Patent application JP 11/012 390 describes a process for recovering a polymer in solution, according to which the said solution is atomized and placed in contact with water vapour to evaporate the solvent residues.
  • this process is applicable only to dilute polymer solutions, since solutions that are too concentrated are too viscous to form droplets by atomization.
  • this process does not allow uniform particles to be obtained when the polymer solution is polluted with heavy products such as certain liquids used during the cleaning of certain plants for manufacturing polymer-based articles or paints.
  • One object of the present invention is consequently to provide a process for recovering a polymer in solution, which makes it possible to process concentrated polymer solutions and/or polymer solutions that are polluted with heavy liquids forming a homogeneous medium therewith, and to provide a resulting product of favourable particle size and with a low residual solvent content.
  • the present invention consequently relates to a process for recovering a polymer in solution in a solvent, possibly in the presence of at least one heavy liquid, the whole forming a homogeneous medium, according to which:
  • the polymer whose recovery is targeted by the process according to the present invention may be of any nature. It may be a thermoplastic resin or an elastomer, but in any case is a resin that may be dissolved in a solvent and that therefore is little or not crosslinked. It may be an unused (or virgin) resin, which has not undergone any melt-forming except for possible granulation, or a used resin (production waste or recycled resin). It may be an apolar polymer, such as an ethylene polymer (PE) or a propylene polymer (PP).
  • PE ethylene polymer
  • PP propylene polymer
  • a polar polymer such as a vinyl chloride polymer (PVC), a vinylidene chloride polymer (PVDC), a vinylidene fluoride polymer (PVDF); an EVOH polymer (copolymer of ethylene and of vinyl alcohol), etc. It may also be a mixture of at least two such polymers of the same nature or of different nature.
  • PVDF vinylidene fluoride homopolymers or copolymers of vinylidene fluoride containing less than 50% by weight of monomer units such as vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, ethylene, etc.
  • PVDC vinylidene fluoride homopolymers or copolymers of vinylidene fluoride containing less than 50% by weight of monomer units such as vinyl fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, hexafluoropropylene, ethylene, etc.
  • the process according to the present invention applies to polymers in solution in a solvent.
  • these articles or particles in suspension should first be dissolved using a solvent whose nature is adapted to that of the polymer to be dissolved and which forms a homogeneous medium with the possible heavy liquids.
  • the solvent in which the polymer is dissolved is generally a liquid having a solubility parameter (a definition of and experimental values for which are given in "Properties of Polymers", D.W. Van Krevelen, 1990 edition, pp. 200-202, and also in “Polymer Handbook", J. Brandrup and E.H. Immergut, Editors, Second Edition, p. IV-337 to IV-359) close to the solubility parameter of the polymer. It is understood that the term "solvent” means either a pure substance or a mixture of substances.
  • a suitable solvent is MEK (methyl ethyl ketone) and in particular an MEK-hexane mixture optionally containing water.
  • the polymer is EVOH, a mixture of water and alcohol (ethanol, methanol, propanol, etc.) is more suitable, and in the case of LDPE, hexane or cyclohexane is preferred.
  • the polymer is PVDF or PVDC, cyclohexanone is suitable for use.
  • solutions that may be processed by the process according to the present invention have a concentration (of polymer and of heavy liquids) such that their viscosity does not disrupt the correct running of the process.
  • the process according to the present invention is applied to a polymer solution free of heavy liquids.
  • adding the non-solvent to the medium generally brings about the precipitation of the polymer and the heterogeneous medium to be atomized consists essentially of a suspension of polymer in a liquid consisting of the solvent and the non-solvent and of possible additives present in the polymer before its dissolution.
  • Working in this way makes it possible to increase the polymer concentration of the solutions to be processed, while having little or no effect on the viscosity of the heterogeneous medium to be atomized.
  • PVC content of more than 150 g per litre of solvent, and even more than 200 g/l in the case of a rigid PVC, or even 300 g/l in the case of a plasticized PVC.
  • Such solutions generally have a viscosity of about from 50 to 1 000 mPa.s or even more at temperatures in the region of 50°C, and they should consequently be brought to a higher temperature (100 or even 200°C) in order to be able to atomize them, which is economically detrimental and may be harmful to the quality of the polymer.
  • Adding a non-solvent makes it possible to reduce this viscosity to a value of less than or equal to 20 mPa.s, preferably to 10 mPa.s, or even to 2 mPa.s, and thus to atomize it at a lower temperature.
  • the amount of non-solvent to be added according to this variant of the invention must be sufficient to bring about the precipitation of the polymer. It thus depends on the nature of the polymer, of the solvent and of the non-solvent, and also on the temperature and pressure conditions.
  • the polymer is PVC and the solvent is MEK, good results have been obtained at a temperature of between 60 and 100°C and at a pressure ranging from atmospheric pressure to 2.2 bar, with solutions containing 300 g of PVC per litre of MEK to which has been added 120 g of water per litre of solution.
  • the precipitation of the solution may be facilitated by reducing the pressure relative to the pressure used during the dissolution, which generally brings about a reduction in temperature.
  • Temperature-sensitive polymers such as EVOH or PVB, for example
  • the precipitation is advantageously performed by adding the non-solvent in an amount that is just sufficient to bring about the total precipitation of the dissolved polymer at the given pressure.
  • the precipitation is performed by the combined injection of non-solvent in liquid form and in gaseous form, which accelerates the precipitation of the polymer.
  • non-solvent injected optionally to contain a small concentration of solvent; this is advantageous since, as outlined hereinbelow, a possible subsequent step of the process can specifically provide such a source of non-solvent, which may thus be reused without any particular purification.
  • a non-solvent that is suitable for use is water. Water in particular gives good results when the polymer to be recovered is PVC. When the polymer to be recovered is PVDF or PVDC, a non-solvent that is suitable for use is methanol.
  • One means for reducing the particle size of the polymer is to add the non-solvent gradually to the solvent containing the dissolved polymer and to apply a large shear rate to the mixture.
  • the process according to the present invention is applied to a polymer solution also comprising at least one heavy liquid that is a non-solvent for the polymer but that is compatible with the solvent so as to form a homogeneous medium.
  • the expression "heavy liquid” is intended to denote a liquid with a boiling point higher than that of the solvent and of the non-solvent.
  • An example of a heavy liquid is white spirit, a cleaning agent used in many fields and in particular in the field of polymer-based paints and coatings.
  • adding a non-solvent to the starting homogeneous medium makes it possible to obtain a heterogeneous medium consisting essentially of an emulsion of the non-solvent in a homogeneous liquid medium consisting of the solvent, the heavy liquid and the dissolved polymer.
  • This emulsion is then readily converted into spherical particles by atomization, whereas direct atomization of the starting homogeneous medium would have led to the formation of non-uniform filaments.
  • the amount of non-solvent to be added according to this variant of the invention must be sufficient to bring about the formation of an emulsion and adequate stirring means are advantageously provided to ensure the stability of this emulsion.
  • the presence of this emulsion allows the atomization of viscous solutions, the viscosity of which also depends on the pressure and temperature conditions and also on the nature of the ingredients of the medium, namely: the polymer, the heavy liquid, the solvent and the non-solvent.
  • the polymer is PVC (and preferably plasticized PVC)
  • the heavy liquid is white spirit
  • the solvent is MEK
  • the non-solvent is water
  • solutions comprising 100 g/l of a "slurry" comprising 50% by weight approximately of PVC plasticized with DOP (dioctyl phthalate) and 50% by weight of white spirit, to which have been added 100 g/l of water.
  • the non-solvent may also contain small amounts of another compound, such as solvent, for example.
  • the liquid medium in homogeneous or heterogeneous form may be freed of one or more of its constituents before heterogenization and/or atomization, and this may be performed by any suitable means.
  • the component(s) with a low boiling point may be removed by simple evaporation.
  • the heterogeneous medium may contain additives initially present in the polymer solution (for example pigments, plasticizers, stabilizers, fillers, etc., present in the polymer before its dissolution).
  • additives initially present in the polymer solution for example pigments, plasticizers, stabilizers, fillers, etc., present in the polymer before its dissolution.
  • the atomization included in the process according to the present invention is performed using any known device, such as a high-pressure nozzle (converting pressure into kinetic energy, the product to be atomized being converted into an unstable film that explodes into fine droplets), by a rotary atomizer (the centrifugal force of a motorized plate creating an unstable film that explodes into fine droplets), by a twin-flow atomizer, by sonication, etc.
  • a high-pressure nozzle converting pressure into kinetic energy, the product to be atomized being converted into an unstable film that explodes into fine droplets
  • a rotary atomizer the centrifugal force of a motorized plate creating an unstable film that explodes into fine droplets
  • twin-flow atomizer by sonication, etc.
  • the gas that vaporizes the solvent is advantageously chosen from air, neutral gases and water vapour.
  • a gas that produces little or no oxidation will advantageously be chosen, such as water vapour or a neutral gas such as nitrogen.
  • Water vapour is particularly suitable for use since, besides its direct calorific supply, its heat of condensation contributes towards very rapid and particularly effective evaporation of the liquid medium present in the droplets. It should be noted that this gas can entrain, by stripping, other possible liquid constituents of the heterogeneous medium (for example the heavy liquid, in the case of the second preferred variant of the present invention).
  • the polymer particles recovered at the atomizer outlet may be subjected to desorption and/or drying, and this may take place in particular when the evaporation gas is water vapour.
  • a gas preferably in a counter-current device or by transportation on a perforated belt through which the gas passes.
  • a major advantage of the process according to the present invention is that it can function in a closed loop, without generating emissions.
  • the vapours collected after the evaporation and/or the entrainment by means of the gas may be condensed and optionally purified by adequate processes (decantation, optionally in the presence of a phase-separating agent; distillation, etc.).
  • the process according to the present invention may be incorporated into any process involving the recovery of a polymer from a solution. In particular, it can form part of a polymer recycling process.
  • the process according to the present invention is applied to a polymer solution obtained by shredding polymer-based articles into fragments with an average size from 1 cm to 50 cm in the event that they exceed these dimensions, and by placing the article fragments in contact with a solvent capable of dissolving the polymer.
  • the polymer is PVC
  • the solvent is an MEK-hexane mixture optionally containing water
  • the non-solvent used to precipitate the polymer is water, as described in patent application EP 945 481 in the name of Solvay.
  • the process according to the present invention is applied to a polymer solution obtained by placing a plastisol slurry (suspension of PVC particles in a plasticizer, diluted with a cleaning liquid such as white spirit) in contact with MEK in an amount sufficient to dissolve the PVC and ensure the formation of a homogeneous liquid medium.
  • a plastisol slurry suspension of PVC particles in a plasticizer, diluted with a cleaning liquid such as white spirit
  • the process according to these two variants of the present invention makes it possible to obtain a very porous powder formed from substantially spherical recycled polymer particles.
  • These particles generally have a mean diameter of less than 100 ⁇ m and preferably less than or equal to 50 ⁇ m. However, it is rare for the mean diameter of these particles to be less than 1 ⁇ m, or even 5 ⁇ m.
  • Such particles may be used in unmodified form in certain applications such as rotary moulding or slush moulding, or may be introduced in unmodified form into a plastisol intended to be coated and gelled. Alternatively, these particles may be granulated in an extruder or, more advantageously, sintered so as to avoid thermal ageing of the polymer.
  • a solution containing 18% by weight of rigid PVC obtained from industrial wastes of window sash frames in solution (at 100°C) in a mixture of 82% MEK/13% hexane/5% water (mass proportions) was first freed of the hexane.
  • Water was then gradually injected therein (0 to 12% by weight relative to the mass of solvent) at 55°C and with stirring (with an intensity adapted to obtain a homogeneous suspension).
  • the heterogeneous medium obtained was then subjected to atomization and the solvent it contains was vaporized by feeding it into a hollow-cone nozzle fed, under 50 to 70 bar, with water vapour (at 100°C and atmospheric pressure) circulating co-currentwise.
  • a powder with a mean diameter of 31 ⁇ m (with 10% of the particles less than 9 ⁇ m in diameter and 90% of the particles less than 60 ⁇ m in diameter) was obtained.
  • a solution containing 28% by weight of plasticized PVC (comprising about 45% PVC, 30% fillers and 25% plasticizers) in solution in a mixture of 82% MEK/13% hexane/5% water (mass proportions) was first freed of the hexane.
  • Water was then gradually injected therein (10 to 12% by weight relative to the mass of solvent) at 55°C and with stirring (with an intensity adapted to obtain a homogeneous suspension).
  • the heterogeneous medium obtained was then subjected to atomization and the solvent it contains was vaporized by feeding it into a hollow-cone nozzle fed, under 50 to 100 bar, with water vapour (at 100°C and atmospheric pressure) circulating co-currentwise.
  • a powder with a particle size of 1 to 100 ⁇ m and a very high porosity was obtained.
  • a solution containing 10% slurry (derived from a coating line and consisting of 50% plastisol and 50% white spirit) and 90% MEK (mass proportions) was prepared and filtered. 10% of water was added thereto at 50°C in order to produce a stable emulsion. These operations were all performed at 50°C and with stirring (with an intensity adapted to obtain a homogeneous emulsion). The emulsion obtained was then atomized at atmospheric pressure in a hollow-cone nozzle into which was injected water vapour co-currentwise.
  • a powder with substantially spherical grains having a particle size of 1 to 100 ⁇ m was collected at the bottom of the apparatus, while the solvent was evaporated off, and the cleaning agent entrained by the water vapour was collected in the top of the apparatus. The same test was repeated without adding the 10% of water for allowing a stable emulsion to be formed; it was not possible to obtain a powder of substantially spherical grains, but only non-uniform filaments.
  • PVDF polyvinyl styrene
  • 1 1 of cyclohexanone 100°C.
  • 2 000 g of methanol were added thereto at 50°C and with stirring (with an intensity adapted to obtain a homogeneous suspension).
  • the suspension obtained was atomized in a hollow-cone nozzle working at a pressure of about 80 bar and fed with water vapour counter-currentwise.
  • the PVDF powder obtained has a mean particle diameter of less than 100 ⁇ m.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Claims (9)

  1. Procédé de récupération d'un polymère en solution dans un solvant, l'ensemble formant un milieu homogène, selon lequel:
    (a) on ajoute un non solvant au milieu homogène de manière à le rendre hétérogène;
    (b) on transforme le milieu hétérogène en des gouttelettes par atomisation;
    (c) on met les gouttelettes en contact avec un gaz qui vaporise le solvant;
    (d) on récupère le polymère sous forme de particules.
  2. Procédé selon la revendication 1, dans lequel le milieu hétérogène est essentiellement constitué d'une suspension de polymère dans un liquide constitué du solvant, du non solvant et des éventuels additifs présents dans le polymère avant sa dissolution.
  3. Procédé selon la revendication 1, dans lequel le milieu hétérogène est essentiellement constitué d'une émulsion du non solvant dans un milieu liquide homogène constitué du solvant, du polymère dissout, des éventuels additifs présents dans le polymère avant sa dissolution et d'un liquide lourd.
  4. Procédé selon la revendication précédente, dans lequel le liquide lourd est du white spirit.
  5. Procédé selon l'une quelconque des revendications précédentes, dans lequel le polymère est le PVC.
  6. Procédé selon la revendication précédente, dans lequel le solvant est la MEK ou un mélange MEK- hexane contenant éventuellement dé l'eau.
  7. Procédé selon l'une quelconque des revendications précédentes, dans lequel le gaz qui vaporise le solvant est de la même nature que le non solvant.
  8. Procédé selon l'une quelconque des revendications précédentes, dans lequel le gaz qui vaporise le solvant est de la vapeur d'eau.
  9. Procédé selon l'une quelconque des revendications précédentes, dans lequel les particules de polymère récupérées sont soumises à une désorption et/ou à un séchage.
EP02791786A 2001-12-11 2002-12-05 Procede de recuperation d'un polymere a partir d'une solution Expired - Lifetime EP1456281B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0116070A FR2833267A1 (fr) 2001-12-11 2001-12-11 Procede de recuperation d'un polymere en solution
FR0116070 2001-12-11
PCT/EP2002/013875 WO2003054064A1 (fr) 2001-12-11 2002-12-05 Procede de recuperation d'un polymere a partir d'une solution

Publications (2)

Publication Number Publication Date
EP1456281A1 EP1456281A1 (fr) 2004-09-15
EP1456281B1 true EP1456281B1 (fr) 2005-11-09

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EP02791786A Expired - Lifetime EP1456281B1 (fr) 2001-12-11 2002-12-05 Procede de recuperation d'un polymere a partir d'une solution

Country Status (16)

Country Link
US (1) US20050010027A1 (fr)
EP (1) EP1456281B1 (fr)
JP (1) JP2005513223A (fr)
KR (1) KR20040073468A (fr)
CN (1) CN1276007C (fr)
AR (1) AR037607A1 (fr)
AT (1) ATE309289T1 (fr)
AU (1) AU2002358103A1 (fr)
BR (1) BR0214851A (fr)
CA (1) CA2469643A1 (fr)
DE (1) DE60207295T2 (fr)
DK (1) DK1456281T3 (fr)
ES (1) ES2252530T3 (fr)
FR (1) FR2833267A1 (fr)
TW (1) TW200408663A (fr)
WO (1) WO2003054064A1 (fr)

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EP2891676A4 (fr) * 2012-08-30 2016-04-06 Toray Industries Procédé de production de particules fines de résine de fluorure de vinylidène et particules fines de résine de fluorure de vinylidène

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FR2857670B1 (fr) * 2003-07-15 2006-02-03 Solvay Procede de recuperation d'un polymere en solution
FR2857669B1 (fr) * 2003-07-15 2005-09-09 Solvay Procede de recuperation d'un polymere en solution
FR2868782B1 (fr) * 2004-04-13 2006-06-16 Solvay Sa Sa Belge Procede de recuperation d'un polymere en solution
US7569658B2 (en) 2004-04-15 2009-08-04 Solvay (Societe Anonyme) Process for the solvent treatment of a plastic
FR2875504B1 (fr) * 2004-09-17 2007-01-12 Solvay Procede pour le traitement d'un melange d abs et de ps
FR2877949B1 (fr) * 2004-11-15 2007-11-23 Solvay Sa Sa Belge Procede d'epuration d'une solution de matiere plastique
FR2878250B1 (fr) 2004-11-22 2007-01-12 Solvay Sa Sa Belge Procede pour l'epuration en metaux lourds de polymeres du chlorure de vinyle (pvc)
FR2878249B1 (fr) 2004-11-22 2007-01-12 Solvay Procede pour l'epuration en metaux lourds de polymeres du chlorure de vinyle (pvc)
FR2889849B1 (fr) * 2005-08-19 2007-10-05 Solvay Procede de recuperation d'un polymere a partir d'un milieu liquide
KR100837426B1 (ko) * 2006-01-20 2008-06-12 주식회사 엘지화학 중합체 정제 방법 및 정제된 중합체
WO2007145765A2 (fr) 2006-06-09 2007-12-21 Dow Corning Corporation Procédé de préparation de résines mq solides sans solvant
JP5339673B2 (ja) * 2006-08-31 2013-11-13 キヤノン株式会社 微粒子の製造方法
FR2906809A1 (fr) * 2006-10-04 2008-04-11 Solvay Procede d'epuration d'un polymere.
GB0619869D0 (en) * 2006-10-07 2006-11-15 Regentec Ltd Porous particles
FR2921372B1 (fr) 2007-09-21 2009-11-13 Solvay Procede de recuperation d'un polymere a partir d'une solution
EP2119741A1 (fr) * 2008-05-09 2009-11-18 SOLVAY (Société Anonyme) Procédé pour recycler des articles basés sur un polymère renforcé à fibre
CN101367957B (zh) * 2008-09-28 2011-09-21 浙江大学 回收聚氯乙烯或偏聚氯乙烯塑料的方法
CN102329429A (zh) * 2010-07-13 2012-01-25 江苏华奥高科技发展有限公司 一种喷盘
HUE044132T2 (hu) * 2013-12-03 2019-09-30 Toray Industries Polivinilidén-fluorid-gyanta-részecskék és eljárás elõállításukra
JP6442925B2 (ja) * 2014-08-26 2018-12-26 日本ゼオン株式会社 水素化ｎｂｒの重合体溶液の濃縮方法
EP3546501A1 (fr) * 2018-03-27 2019-10-02 Friedrich-Alexander-Universität Erlangen-Nürnberg Procédé de production d'une population de particules de difluorure de polyvinylidène ou de particules d'un copolymère comprenant du difluorure de polyvinylidène
WO2023117971A1 (fr) * 2021-12-23 2023-06-29 Solvay Specialty Polymers Italy S.P.A. Procédé de purification de polymères de fluorure de vinylidène

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2891676A4 (fr) * 2012-08-30 2016-04-06 Toray Industries Procédé de production de particules fines de résine de fluorure de vinylidène et particules fines de résine de fluorure de vinylidène
US9920193B2 (en) 2012-08-30 2018-03-20 Toray Industries, Inc. Method for producing polyvinylidene difluoride particles, and polyvinylidene difluoride particles

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KR20040073468A (ko) 2004-08-19
EP1456281A1 (fr) 2004-09-15
DK1456281T3 (da) 2006-03-27
FR2833267A1 (fr) 2003-06-13
ES2252530T3 (es) 2006-05-16
CN1602329A (zh) 2005-03-30
CA2469643A1 (fr) 2003-07-03
DE60207295D1 (de) 2005-12-15
WO2003054064A1 (fr) 2003-07-03
DE60207295T2 (de) 2006-07-20
AR037607A1 (es) 2004-11-17
CN1276007C (zh) 2006-09-20
BR0214851A (pt) 2004-12-14
US20050010027A1 (en) 2005-01-13
AU2002358103A1 (en) 2003-07-09
ATE309289T1 (de) 2005-11-15
TW200408663A (en) 2004-06-01
JP2005513223A (ja) 2005-05-12

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